Lubrication of spandex yarns



United States Patent Ofitice 3,548,047 Patented Dec. 15, 1970 US. Cl. 264-136 Claims ABSTRACT OF THE DISCLOSURE A method for handling spandex yarn after wet spinning wherein the yarn is passed through an aqueous bath containing a small amount of a water-soluble, nonhydrolyzable siloxane-oxyalkylene copolymer.

In the production of spandex yarns, it is common to use a so-called wet-spinning process wherein spandex filaments are extruded or spun into a coagulating bath. After the coagulating bath, it is known to paSs the filaments through an aqueous wash bath in order to extract excess solvent from the filaments prior to further processing. After coagulation and washing of the filament yarn, various processing steps are possible before the final windup of the yarn as a package or spool. It is customary to apply a lubricating dressing to the yarn just prior to the final wind-up in order to condition the yarn for further handling. This lubricant keeps the yarn from blocking or sticking together and from sticking to the machinery used in needling or otherwise utilizing the yarn.

In our processing of the yarn between the aqueous bath and the final wind-up, we prefer to use a drying step wherein the yarn is dried, preferably on a heated roller. This drying precedes the customary lubrication step and we have found that the yarn tends to stick on the drying rolls and to not align properly on the roller, thereby putting the yarn under tension and eventually breaking the yarn and interrupting the process. We attempted to solve this problem by applying the customary lubricants, such as mineral oil or the like, just after the yarn emerged from the aqueous wash bath. This proved unsatisfactory, however, because these lubricants tend to decompose and smoke on the drying rolls. The decomposition products tend to build up on the rollers, thereby interfering with the alignment of the yarn and creating tension and eventual breakage of the yarn.

We have now discovered that we can condition the yarn for further treatment after the aqueous extraction bath by adding to the water bath a small quantity of a water-soluble non-hydrolyzable siloxane-oxyalkylene block copolymer as hereinafter characterized. We find that this addition causes the yarn to handle well throughout processing prior to final Wind-up and that yarn so treated aligns well on the drying rolls without the tension and breakage otherwise encountered.

Furthermore, we have realized several additional unexpected benefits from the addition off siloxane-oxyalkylene block copolymer to the aqueous bath. We have found that use of our additive in the water bath decreases the quantity of conventional lubricant needed prior to wind-up by at least 50 percent. Our additive also serves as anti-static agent on the yarn and eliminates the need for adding such an agent to the conventional lubricant. We have also found to our surprise that yarn treated according to our process releases better from the package or spool than does yarn treated only with a conventional lubricant.

We have found that at least 0.01 percent of the siloxaneoxyalkylene block copolymer by weight of the aqueous bath must be used to obtain appreciable results, while a minimum of about 0.05 percent is preferred. The only real limit on the quantity to be added is that at very high concentrations, that is, those much above about 1 percent, undesirable side-effects may be encountered. We prefer to use from about 0.05 percent to about 0.1 percent by weight of the total bath. The block copolymer in the wash bath must, of course, be replenished as the yarn passing through the bath picks up the block copolymer and draws it out of the bath.

The siloxane-oxyalkylene copolymers useful in this invention are of the class that are known as block copolymers. Block copolymers are composed of at least two sections or blocks, at least one section or block composed of one type of recurring units or groups (e.g., siloxane units as in the copolymers useful in this invention) and at least one other section or block composed of a different type of recurring units or groups (e.g., oxyalkylene groups as in the copolymers useful in this invention). The copolymers useful in this invention contain one or more siloxane blocks and one or more oxyalkylene blocks.

The siloxane blocks in the block copolymers useful in this invention contain at least two siloxane units that are represented by the formula 1 R ,SiO

wherein R is a monovalent hydrocarbon group, a halogensubstituted monovalent hydrocarbon group, or a divalent hydrocarbon group and b has a value from 1 to 3 inclusive. Preferably, each R contains from one to about twenty carbon atoms. The groups represented by R can be the same or different in any given siloxane unit or throughout the siloxane block, and the value of b in the various siloxane units in the siloxane block can be the same or different. The divalent groups represented by R link the siloxane block to the oxyalkylene block. Each siloxane block contains at least one group represented by Formula 1 wherein at least one group represented by R is a divalent hydrocarbon group which joins the siloxane block to the oxyalkylene block. The siloxane block has a ratio of hydrocarbon groups to silicon atoms from 1:1 to 3: 1.

Illustrative of the monovalent hydrocarbon groups that are represented by R in Formula 1 are the alkenyl groups (for example, the vinyl group and the allyl group); the cycloalkenyl groups (for example, the cyclohexenyl group); the alkyl groups (for example, the methyl, ethyl, isopropyl, octyl, dodecyl, octadecyl and eicosyl groups); the aryl groups (for example, the phenyl, naphthyl and terphenyl groups); the aralkyl groups (for example, the benzyl and the phenylethyl groups); the alkaryl groups (for example, the styryl, tolyl, and n-hexylphenyl groups); and the cycloalkyl groups (for example, the cyclohexyl group).

Illustrative of the halogen-substituted monovalent hydrocarbon groups that are represented by R in Formula 1 are the chloromethyl, trichloroethyl, perfluorovinyl, perfluoropropyl, para-bromobenzyl, iodophenyl, alphachloro-beta-phenylethyl, para-chlorotolyl and bromocyclohexyl groups and the like.

Illustrative of the divalent hydrocarbon groups represented by R in Formula 1 are the alkylene groups (such as the methylene, ethylene, propylene, butylene, 2,2-dimethyl-1,3-propylene, decylene and eicosylene groups), the arylene groups (such as the phenylethylene group). Preferably, the divalent hydrocarbon group is an alkylene group containing from two to four successive carbon atoms. Siloxane groups containing divalent hydrocarbon groups as substituents are illustrated by groups having the formulas:

These divalent hydrocarbon groups are linked to a silicon atom of the siloxane block by a silicon-to-carbon bond and to an oxygen atom of the oxyalkylene block by a carbon-to-oxygen bond.

The siloxane block can contain siloxane units that are represented by Formula 1 wherein either the same hydrocarbon groups are attached to a silicon atom (e.g., the dimethylsiloxy, diphenylsiloxy and diethylsiloxy groups) or different hydrocarbon groups are attached to a silicon atom (e.g., the methylphenylsiloxy, phenylethylmethylsiloxy and ethylvinylsiloxy groups).

The siloxane block in the block copolymers useful in this invention can contain one or more types of siloxane units that are represented by Formula 1 provided that at least one group has at least one divalent hydrocarbon substituent. By way of illustration, only ethylenemethylsiloxy groups can be present in the siloxane block or the siloxane block can contain more than one type of siloxane group, e.g., the block can contain both ethylene methylsiloxy groups and diphenylsiloxy groups, or the block can contain ethylenemethylsiloxy groups, diphenylsiloxy groups and diethylsiloxy groups.

The siloxane block contained in the block copolymers useful in this invention can contain trifunctional siloxane units (e.g., monomethylsiloxane groups, CH SiO difunctional siloxane groups (e.g., dimethylsiloxane groups (CH SiO), monofunctional siloxane units (e.g., trimethylsiloxane units, (CH SiO or combinations of these types of siloXane units having the same or different substituents. Due to the functionality of the siloxane groups, the siloxane block can be predominately linear or cyclic or crosslinked or it can have combinations of these structures.

The siloxane block contained in the block copolymers useful in this invention can contain organic end-blocking or chain terminating organic groups as well as the monofunctional siloxane chain terminating groups encompassed by Formula 1. By way of illustration, the siloxane block can contain each organic end-blocking groups as the hydroxyl group, the aryloxy groups (such as the phenoxy group), the alkoxy groups (such as the methoxy, ethoxy, propoxy and butoxy groups), the acyloxy groups such as the acetoxy group, and the like.

The siloxane blocks in the block copolymers useful in this invention each contain at least two siloxane units that are represented by Formula 1. Preferably, the siloxane blocks contain a total of at least three siloxane units that are represented by Formula 1 and by Formula 2 below. That part of the average molecular weight of the copolymer that is attributable to the siloxane blocks can be as high as 50,000 or greater.

A siloxane block can contain, in addition to the groups represented by Formula (1), one or more siloxane units represented by the formula: liIt R,,SiO (2) 2 wherein R has the meaning defined in Formula 1, e has a value from 0 to 2, f has a value from 1 to 2 and e plus 1 has a value from 1 to 3.

The oxyalkylene blocks in the block copolymers useful in this invention each contain at least one oxyalkylene group represented by the Formula:

wherein R is an alkylene group. Preferably, the alkylene group represented by R in Formula 3 contains from two to about ten carbon atoms, and most preferably from two to three carbon atoms. Illustrative of the oxyalkylene groups that are represented by Formula 3 are the oxyethylene, oxy-1,2-propylene, oxy-l,3-propylene, oxy-2,2- dimethyl-l,3-propylene, oXy-1,10-decylene groups, and the like.

The oxyalkylene blocks in the block copolymer useful in this invention can contain one or more of the various types of oxyalkylene groups represented by Formula 3. By way of illustration, the oxyalkylene blocks can contain only oxyethylene or only oxypropylene groups or both oxypropylene groups and oxyethylene groups, or other combinations of the various types of oxylkylene groups represented by Formula 3.

The oxyalkylene blocks in the block copolymers useful in this invention can contain organic end-blocking or chain terminating groups. By way of illustration, the oxyalkylene blocks can contain such end-blocking groups as the hydroxy group, the aryloxy group (such as the phenoxy group), the alkoxy groups (such as the methoxy, ethoxy, propoxy and butoxy groups), alkenyloxy groups (such as the vinyloxy and the allyloxy groups). Also a single group can serve as an end-block group for more than one oxyalkylene block. For example, the glyceroxy group a. a. a,

I l l can serve as an end-blocking group for three oxyalkylene chains.

The oxyalkylene blocks in the block copolymers useful in this invention each contain at least one oxyalkylene groups that are represented by Formula 3. Preferably, each block contains at least five such groups. That part of the average molecular weight of the copolymer that is attributable to the oxyalkylene blocks can be 50,000 or greater.

The oxyalkylene block can contain a carbonyl group Such groups can be present at the end of the block, e.g., when the copolymer is produced from a carboxy alkylsiloxane (or a derivative thereof) and an oxyalkylene compound. Thus the following structures can be present in the copolymers:

The block copolymers useful in this invention can contain siloxane blocks and oxyalkylene blocks in any relative amount. The copolymer can contain, for example, from 5 parts by weight up to parts by weight of siloxane blocks and from 5 parts by weight to 95 parts by Weight of oxyalkylene blocks per parts by weight of the copolymer. Preferably, the copolymer contain 5 parts by weight to 50 parts by weight of the siloxane blocks and from 50 parts by weight to 95 parts by weight of the oxyalkylene blocks per 100 parts by weight of the copolymer.

The block copolymers useful in this invention can contain more than one of each of the blocks and the blocks can be arranged in various configurations such as linear, cyclic or branched configurations. By way of illustration, the following classes of compounds are among the siloxane-oxyalkylene block copolymers useful in this invention:

(A) Copolymers that contain at least one unit that is represented by the formula:

(B) Copolymers that contain at least one unit that is represented by the formula: h is O SiGO(GO)nGSiO (C) Copolymers that contain at least one unit that is represented by the formula:

In the above Formulas 4, 5 and 6, G is a monovalent hydrocarbon radical, or halogen-substituted monovalent hydrocarbon radical, G is a divalent hydrocarbon radical, G" is an alkylene radical containing at least two carbon atoms, G is a hydrogen atom or a monovalent hydrocarbon radical free of aliphatic unsaturation, n is an integer having a value of at least four, and c has a value from to 2 in Formulas 4, and and a value from 0 to 1 in Formula 6. In Formulas 4, 5, and 6, G can represent the same or different radicals, n preferably has a value from 5 to 30 and G" can represent the same or different radicals, i.e., the group (OG") can represent, for example, the groups: -(OC H 2 4)p( 3 6)q (CH3H6)11" -(OC H (OC H where p and q are integers.

The monovalent hydrocarbon radicals and halogensubstituted monovalent hydrocarbon radicals represented by G in Formulas 4, 5, and 6, can be saturated or olefinically unsaturated or can contain benzenoid unsaturation. Illustrative of the monovalent hydrocarbon radicals represented by G are the linear aliphatic radicals (e.g., the methyl, ethyl, decyl, octadecyl and eicosyl radicals), the cycloaliphatic radicals (e.g., the cyclohexyl and the cyclopentyl radicals), the aryl radicals (e.g., the phenyl, tolyl, xylyl, naphthyl and terphenyl radicals), the aralkyl radicals (e.g., the benzyl and betaphenylethyl radicals), the unsaturated linear aliphatic radicals (e.g., the vinyl, allyl and hexenyl radicals) and the unsaturated cycloaliphatic radicals (e.g., the cyclohexenyl radical).

Illustrative of the halogen-substituted monovalent hydrocarbon radicals represented by G are the chloromethyl, trichloroethyl, perfluorovinyl, para-bromobenzyl, idophenyl, alphachloro-betaphenylethyl, parachlorotolyl and bromocyclohexyl groups and the like.

Preferably, the G and G groups (included in the definition of R in Formulas 1 and 2 above) contain from one to twenty carbon atoms and the G groups (included in the definition of R in Formula 3 above) contain from two to about ten carbon atoms. When the G groups is a monovalent hydrocarbon radical free of aliphatic unsaturation it preferably contains from one to about twelve carbon atoms.

Illustrative of the divalent hydrocarbon radicals represented by G in Formulas 4, 5, and 6, are the alkylene radicals (e.g., the methylene, ethylene, 1,3-propylene, 1,4-

butylene, 1,12-dodecylene and 1,20-eicosylene radicals), and the arylene radicals (e.g., the phenylene radical), and the alkarylene radicals (e.g., the phenylethylene radicals). In Formulas 4, 5, and 6, G is preferably an alklene radical containing at least two carbon atoms.

Illustrative of the alkylene radicals containing at least two carbon atoms represented by G" in Formulas 4, 5, and 6 are the ethylene, 1,2-propylene, l,3-pr0pylene, 1,6- hexylene, 2-ethylhexylene-l,6 and 1,10-decylene radicals.

Illustrative of the radicals represented by G' in Formulas 4, 5, and 6, are the saturated linear or branched chain aliphatic hydrocarbon radicals (e.g., the methyl, ethyl, propyl, n-butyl, tert.-butyl, and decyl radicals), the saturated cycloaliphatic hydrocarbon radicals (e.g., the cyclopentyl and cyclohexyl radicals), the aryl hydrocarbon radicals (e.g., the phenyl, tolyl, naphthyl and xylyl radicals) and the aralkyl hydrocarbon radicals (e.g., the benzyl and beta-phenylethyl radicals).

Among the siloxane-oxyalkylene block copolymers that are especially suited for use in this invention are those having the formula:

wherein Me is a methyl group, In has a value from 0 to 25 inclusive, n has a value from 1 to 10 inclusive, x has a value from 3 to 25 inclusive, y has a value from 0 to 25 inclusive, z has a value from 2 to 3 inclusive and R" is an alkyl group containing from 1 to 4 carbon atoms inclusive. I

Particularly useful are copolymers of the following formulas:

EXAMPLE 1 Spandex yarn of denier was spun from a dimethylformamide solution which contained 20 percent by weight of a polyester-based polyurethane-urea spandex polymer, pigmented with TiO The spandex polymer was made from polycaprolactone diol, p,p-methylene diphenyl diisocyanate and ethylenediamine. The yarn was spun into a coagulation bath of water and dimethylforrnamide and then passed into a hot aqueous wash bath containing 0.1 percent, by weight of the bath, of a water-soluble nonhydrolyzable siloxane-oxyalkylene block copolymer of the Formula I above. The yarn was then dried over a heated roll and then lubricated with a kiss roll with 3.6 percent by weight of a finish consisting of 84 percent by weight commercial mineral oil and 16 percent isopropanolamine oleate, prior to final winding onto a take-up package. Yarns thus treated released freely from the take-up package, over the end, and were knitted bare, without breakage.

EXAMPLE 2 Spandex yarn of 140 denier was spun from a dimethylformamide solution which contained 20 percent by weight of a polyester-based polyurethane-urea spandex polymer, pigmented with TiO The spandex polymer was made from polycarprolactone diol, p,p'-methylene diphenyl diisocyanate and ethylenediamine. The yarn was spun into a coagulation bath of water and dimethylformamide and then passed into a hot aqueous wash bath containing 0.1 percent, by weight of the bath, of a water-soluble nonhydrolyzable siloxane-oxyalkylene block copolymer of the Formula IV above. The yarn was then dried over a heated roll and then wound onto a take-up package. Yarns thus treated released freely from the take-up package, over the end, and were knitted bare with fair results. When a conventional mineral oil lubricant was applied prior to knitting the knitting properties were improved from. fair to good.

EXAMPLE 3 Spandex yarn of 140 denier was spun from a dimethylformamide solution which contained 20 percent by Weight of a polyester-based polyurethane-urea spandex polymer, pigmented with TiO and containing stabilizer additives for protection from the degrading effects of ultraviolet light and oxidation. The spandex polymer was made from polycaprolactone diol, p,p-methylene diphenyl diisocyanate and ethylenediamine. The yarn was spun into a coagulation bath of water and dimethylformamide and then passed into a hot aqueous wash bath containing 0.4 percent, by weight of the bath, of a commercial lubricant, an emulsified mineral oil. The yarn stuck on the drying roll, smoked and built up decomposition product on the drying roll. Continual operation would obviously have resulted in eventual breakage of the yarn. The yarn thus made would not knit, even with a support yarn and released poorly from the package. When additional lubricant was added before knitting the yarn could be knitted poorly with support yarn and not at all without. It still gave poor package release.

When yarn was made in the above manner but with 0.1 percent, by weight of the bath, of a water-soluble nonhydrolyzable siloxane-oxyalkylene block copolymer of the Formula IV above added, the knitting properties of the yarn were not improved but it gave excellent release from the package. This demonstrates the value of the silicone copolymer in improving package release.

What is claimed is:

1. In a process for wet spinning polycaprolactone-based polyurethane-urea spandex yarn, wherein filaments are spun into a coagulating bath in which a filament yarn is formed and said filament is then removed from said coagulating bath and passed through an aqueous wash bath to extract excess solvent, the improvement which comprises employing in said aqueous bath at least 0.01 percent, by weight of said bath, of a water-soluble, non-hydrolyzable siloxane-oxyalkylene block copolymer consisting essentially of (a) at least one siloxane block containing at least two siloxane units represented by the formula:

RbSiO 7 wherein each R group contains from one to about twenty carbon atoms and is selected from the class consisting of monovalent hydrocarbon groups, halogen-substituted monovalent hydrocarbon groups and divalent hydrocarbon groups and b has a value from 1 to 3 inclusive, said siloxane block containing at least one of said siloxane units wherein at least one R group is a divalent hydrocarbon group, and (b) at least one oxyalkylene block containing at least one oxylkylene group represented by the formula RO-, wherein R is an alkylene group containing from two to about ten carbon atoms, said siloxane and oxyalkylene blocks being interconnected by said divalent hydrocarbon group.

2. A process according to claim 1 wherein said aqueous bath contains from about 0.01 to about 1.0 percent by weight of said bath, of said siloxane-oxyalkylene copolymer.

3. A process according to claim 1 wherein said aqueous bath contains from about 0.05 to about 0.1 percent, by weight of said bath, of said siloxane-oxyalkylene copolymer.

4. In a process for wet spinning polycaprolactone-based polyurethane-urea spandex yarn wherein filaments are spun into a coagulating bath in which a filament yarn is formed and said filament yarn is then removed from said coagulating bath and passed through an aqueous wash bath to extract excess solvents, the improvement which comprises employing in said aqueous bath at least 0.01 percent, by weight of said bath, of a water-soluble, nonhydrolyzable siloxane-oxyalkylene block copolymer having the formula:

wherein Me is a methyl group, In has a value from 0 to 25 inclusive, n has a value from 1 to 10 inclusive, x has a value from 3 to 25 inclusive, y has a value from O to 25 inclusive, 1 has a value from 2 to 3 inclusive and R" is an alkyl group containing from 1 to 4 carbon atoms inclusive.

5. A process according to claim 4 wherein said aqueous bath contains from about 0.01 to about 1.0 percent, by weight of said bath, of said siloxane-oxyalkylene copolymer.

6. A process according to claim 4 wherein said aqueous bath contains from about 0.05 to about 0.1 percent, by weight of said bath, of said siloxane-oxyalkylene copolymer.

7. A process according to claim 6 wherein said siloxaneoxyalkylene copolymer has the formulas:

8. A process according to claim 6 wherein said siloxaneoxyalkylene copolymer has the formula:

9. A process according to claim 6 wherein said siloxaneoxyalkylene copolymer has the formula:

10. A process according to claim 6 wherein said siloxane-oxyalkylene copolymer has the formula:

(3H3 (C Da K ahSioltzl fla 3 00M9(021140)2oCt e? l5.i (C 3) References Cited UNITED STATES PATENTS 2,079,133 5/1937 Taylor.

3,161,706 12/1964 Peters 264 (urethane) 3,339,000 8/1967 Vance 264181X 3,383,366 5/1968 Taub 260- 3,388,200 6/1968 Jackson et al. 264178b 3,296,063 1/1967 Chandler 264-211X 3,336,428 8/1967 Walter et al. 264184X 3,377,308 4/1968 Oertel et al. 260-326 3,419,653 12/1968 Briggs et al. 264-204 JULIUS FROME, Primary Examiner I. H. WOO, Assistant Examiner US. Cl. X.R.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3 548, 047 Dated December 15, 1970 Inventor(s) A. P. Jones Jr. & G. M. Bryant It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 4, line 29, "oxylkylene" should be -oxyalkylene--. Column 5, line 42, formula (OG") should read --(0G") Column 5, line 44, that portion of the formula reading -(CH3H6) should read C3 6)p- Column 6, line 34, that portion of formula (I) reading H (OC3C0 H should read as follows Column 6, line 48, that portion of formula (IV) reading 2 4 )20 3 $i] Si(CH should read as follows-- Column 7, line 65, "oxylkylene" should read -oxya1kylene-- Claim 4, the formula should read as follows-- Claim 10, the formula should read as follows c Signed and sealed this 15th day of June 1971 (SEAL) Attest:

EDWARD M.FLETGHER,JR. WILLIAM E. SGHUYLEH Attesting Officer Commissions r of Pat FORM PO-IOSD (10-69) 

